Methods for recovering and/or removing reagents from porous media

ABSTRACT

A composition and method for displacing, dissolving, extracting, recovering, and/or removing solvent and/or any solvent-associated liquids from a solvent-treated material or penetrating through pores or the surface of a solvent-treated material using a solvent-extracting composition for contacting solvent-treated material and separating the solvent and any solvent-associated liquids from the solvent-treated material as well as the solvent-extracting composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 35 U.S.C. §371 National Phase Entry Applicationfrom PCT/US2013/024491, filed Feb. 1, 2013, and designating the UnitedStates, which claims the benefit of U.S. Provisional Application No.61/594,129 filed Feb. 2, 2012, the entire disclosures of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to the field of removal, displacement,dissolution, extraction, or penetration through pores or surface of amaterial containing solvent trapped in its pores after a process ofextracting hydrocarbons from the material or solvent treatment of thematerials.

BACKGROUND OF THE INVENTION

Processes for the devulcanization of rubber, as well as theliquefaction, solubilization and/or extraction of hydrocarbon-containingorganic matter from hydrocarbon-containing materials, using turpentineliquids have been developed as described in U.S. Pat. No. 7,767,722 andU.S. Pat. No. 8,101,812. Processes for the recycling of plasticscomprising polymers via solvent treatment have been developed asdescribed in PCT Pub. No. WO 2012/033742. However, because a substantialportion of the solvents, e.g., turpentine liquids, remain trapped withinthese materials after treatment, there remains a need in the art for amethod of dissolving, extracting, and/or removing solvents such asturpentine liquids from the turpentine liquid-treated rubbers, plastics,and hydrocarbon-containing materials.

Devulcanized rubber, rubber, partially devulcanized rubber, plasticscontaining polymers, recycled plastics, recovered plastics, siliconsubstrates, limestone, natural and synthetic porous materials, mineraland rock formations, sponges, and hydrocarbon-containing materials thathave been treated with solvents may contain various amounts of thosesolvents trapped within the pores of the materials, plastics, or rubber.In order to further use or process these materials, it is necessary toremove the trapped solvents and liquids that are associated with thetrapped solvents. Further, in order to effect economical processes, itis advantageous to remove and recycle as much of the trapped solvents aspossible for reuse.

The liquefaction, solubilization and/or extraction of fossil fuels, alsocalled hydrocarbon-containing organic matter, in solid, semi-solid,highly viscous or viscous form (individually and jointly referred to asfossil fuels hereafter) have proven to be extremely challenging anddifficult. As used herein, such fossils fuels include, but are notlimited to, hydrocarbon-containing organic matter within coal, oilshale, tar (oil) sands and oil sands (hereinafter referred to as “tar(oil) sands,” “tar sands,” or “oil sands,” interchangeably), as well ascrude oil, heavy or extra heavy crude oil, natural gas and petroleumgas, crude bitumen, kerogen, natural asphalt and/or asphalteneshydrocarbon. The difficulty can in part be attributed to the fact thatthese fossil fuels include complex organic polymers linked by oxygen andsulfur bonds, which are often imbedded in the matrices of inorganiccompounds. A need exists to produce additional liquid hydrocarbon feedstock for the manufacture of liquid and gaseous fuels as well as for theproduction of various chemicals, pharmaceuticals and engineeredmaterials as the demand and consumption for hydrocarbon based materialsincreases.

SUMMARY OF INVENTION

In accordance with one embodiment of the present invention, the presentinvention provides a method for displacing, removing and recoveringtrapped reagents such as solvents and/or associated liquids that arecontained in rubber, plastics, hydrocarbon-containing material, or anyother type of material or other porous material that has such reagentstrapped within its pores. The materials may include, but are not limitedto rubber, devulcanized rubber, partially devulcanized rubber, plasticscontaining polymers, recycled plastics, recovered plastics, siliconsubstrates, limestone, natural and synthetic porous materials, mineraland rock formations, sponges, waste, and hydrocarbon-containingmaterials. Hydrocarbon-containing organic matter includes, but is notlimited to, heavy crude oil, crude oil, oil shale, tar (oil) sands,coal, bitumen, and the like. Exemplary hydrocarbon-containing materialscan also include oil tank bottoms, oil pit or pond sludge and slurrymix, discarded foods, manure, sewage sludge or municipal garbage. Forexample, the material has previously been treated with a solvent(hereinafter the material will be referred to as the “solvent-treatedmaterial”) and optionally also treated with associated liquids such aslower aliphatic alcohols, alkanes, aromatics, aliphatic amines, aromaticamines, carbon bisulfide and mixtures thereof. “Solvent-associatedliquids” may also include hydrocarbons, sulfur-containing materials,polymers, and other compounds from within the material that have beendissolved into the solvent, and which remain trapped within thesolvent-treated material.

The method includes the steps of providing an alcohol, an organiccompound with a hydroxyl functional group, and/or one or more commonsolvents such as an organic or inorganic solvent, and contacting thesolvent-treated material with the alcohol, or a mixture of the alcoholwith an organic compound with one or more hydroxyl functional group(s)and/or an organic or inorganic solvent, such that a recovery mixture isformed, as well as residual material. The recovery mixture contains atleast a portion of the solvent that was trapped within thesolvent-treated material (hereinafter referred to as the “trappedsolvent”) and at least one of the alcohol, the organic compound with oneor more hydroxyl functional group(s), and/or organic or inorganicsolvent. The residual material includes non-soluble material from thesolvent-treated material. The residual material can also include areduced portion of the trapped solvent in the circumstance where allsuch trapped solvent has not been solubilized by the alcohol, theorganic compound with a hydroxyl functional group, and/or organic orinorganic solvent, and moved into the recovery mixture. The residualmaterial is then separated from the recovery mixture. The recoverymixture is further separated into a first portion and a second portion.The first portion of the recovery mixture includes a trapped solventproduct stream that includes at least a portion of the trapped solventextracted from the solvent-treated material. The second portion of therecovery mixture includes at least a portion of the alcohol, the organiccompound with a hydroxyl functional group, and/or organic or inorganicsolvent. In one embodiment, substantially all of the trapped solvent isrecovered in the recovery mixture.

In another embodiment, the present invention provides a composition forextracting, removing and recovering trapped solvent and other associatedliquids that are contained in rubber or hydrocarbon-containing materialthat has been treated with a solvent, e.g., a turpentine liquid. Thecomposition, which hereinafter will be referred to as the“solvent-extracting composition” can include one or more of an alcohol,the organic compound with a hydroxyl functional group, and/or organic orinorganic solvent.

A method of extracting hydrocarbon-containing organic matter from ahydrocarbon-containing material is provided, which includes the steps ofproviding a first liquid including a turpentine liquid and contactingthe hydrocarbon-containing material with the turpentine liquid such thatan extraction mixture is formed, as well as residual material. Theextraction mixture contains at least a portion of thehydrocarbon-containing organic matter and the turpentine liquid. Theresidual material includes non-soluble material from thehydrocarbon-containing material. The residual material can also includea reduced portion of the hydrocarbon-containing organic matter in thecircumstance where all such hydrocarbon-containing material has not beensolubilized by the turpentine liquid and moved into the extractionmixture. The residual material is then separated from the extractionmixture. The extraction mixture is further separated into a firstportion and a second portion. The first portion of the extractionmixture includes a hydrocarbon product stream that includes at least aportion of the hydrocarbon-containing organic matter extracted from thehydrocarbon-containing material. The second portion of the extractionmixture includes at least a portion of the turpentine liquid. In oneembodiment, at least a portion of the turpentine liquid is recycled tothe hydrocarbon-extracting liquid.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention relates to a readily deployedcomposition for the dissolution, extraction, or penetration throughpores or surface of a material containing solvent and associated liquidstrapped in pores of a solvent-treated material (the “solvent-extractingremoving composition”). The present invention also relates to a readilydeployed composition for use in a process for extraction, liquefactionand/or solubilization of fossil fuels from coal, oil shale, crude oil,and tar (oil) sands.

According to one embodiment, a method is provided including the steps ofdisplacing, dissolving, extracting, recovering, removing, and/orpenetrating through the pores or surface of a material containingsolvent trapped in its pores after a process of extracting hydrocarbonsfrom the material. The material containing trapped solvent may have beenpreviously treated with turpentine liquid. Examples of such materialsare plastics, coal, oil shale, tar (oil) sands, a reservoir containingcrude oil, crude oil, natural gas (which frequently coexists with crudeoils and other said fossil fuels), rubber that has been devulcanizedusing turpentine liquid, or a combination thereof. The materialcontaining turpentine liquids can be solid, semi-solid, liquid, sludge,viscous liquid, or liquid. Other such materials can also includesolvent-treated oil tank bottoms, oil pit or pond sludge and slurry mix,discarded foods, manure, sewage sludge or municipal garbage.

Displacing, extracting, recovering, removing, and/or penetrating throughthe pores or surface of a material containing solvent and associatedliquids trapped in the pores of the material, which has been treatedwithin the material includes the step of providing a solvent-extractingcomposition comprising, consisting essentially of, or consisting of analcohol, an organic compound with a hydroxyl functional group, and/or anorganic or inorganic solvent and contacting the turpentineliquid-treated material with the solvent-extracting composition suchthat a recovery mixture is formed, as well as residual material. In someembodiments, the solvent-extracting composition is aturpentine-extracting composition.

According to the present invention, the quantity of solvent trappedwithin the solvent-treated material is substantially reduced. Forexample, after devulcanization using a devulcanization fluid, thedevulcanized rubber may contain up to about 50% of the devulcanizationfluid trapped within its pores. According to the method describedherein, a significant percentage of the devulcanization fluid can beextracted from the pores of the devulcanized rubber, e.g., at least 60%,70%, 80%, 90% and up to 100% of the devulcanization fluid can be removedfrom the pores.

In one embodiment, the solvent is displaced, extracted, recovered, orremoved using an alcohol, an organic compound with a hydroxyl functionalgroup, and/or organic or inorganic solvent. Examples of solvents thatcan be displaced, extracted, recovered, or removed are turpentineliquids such as natural turpentine, synthetic turpentine, mineralturpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol,beta-terpineol, gamma-terpineol, 3-carene, anethole, dipentene(p-mentha-1,8-diene), terpene resins, alpha-terpene, beta-terpene, gammaterpene, nopol, pinane, camphene, p-cymene, anisaldehyde, 2-pinanehydroperoxide, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, terpinhydrate, ocimene, 2-pinanol, dihydromyrcenol, isoborneol, alloocimene,alloocimene alcohols, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane,camphor, p-menthan-8-ol, alpha-terpinyl acetate, citral, citronellol,7-methoxydihydrocitronellal, 10-camphorsulphonic acid, p-menthene,p-menthan-8-yl acetate, citronellal, 7-hydroxydihydrocitronellal,menthol, menthone, polymers thereof, or mixtures thereof, alkanes,aromatics, aliphatic amines, aromatic amines, carbon bisulfide, solventsmanufactured in petroleum refining, such as decant oil, light cycle oiland naphtha, solvents manufactured in dry distilling coal andfractionating liquefied coal, benzene, naphthalene, toluene, pentane,heptane, hexane, benzene, toluene, xylene, naphthalene, anthracene,tetraline, triethylamine, aniline, carbon bisulfide, and mixturesthereof.

In one embodiment, the solvent-extracting composition contains one ormore acyclic or cyclic alcohols. For example, the alcohol can be simplealcohols such as methanol (methyl alcohol), ethanol (ethyl alcohol),propanol (propyl alcohol), isopropanol, butanol, isobutanol, pentanoland its eight more isomers (1-Pentanol, 3-Methyl-1-butanol,2-Methyl-1-butanol, 2,2-Dimethyl-1-propanol, 3-Pentanol, 2-Pentanol,3-Methyl-2-butanol, 2-Methyl-2-butanol) and hexanol and its sixteen moreisomers (1-Hexanol, 2-Hexanol, 3-Hexanol, 2-Methyl-1-pentanol,3-Methyl-1-pentanol, 4-Methyl-1-pentanol, 2-Methyl-2-pentanol,3-Methyl-2-pentanol, 4-Methyl-2-pentanol, 2-Methyl-3-pentanol, Tertiary3-Methyl-3-pentanol, Primary 2,2-Dimethyl-1-butanol,2,3-Dimethyl-1-butanol, 3,3-Dimethyl-1-butanol, 2,3-Dimethyl-2-butanol,3,3-Dimethyl-2-butanol, 2-Ethyl-1-butanol), lower aliphatic alcohols, ora mixture thereof. In certain embodiments, the alcohol is methanol(methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol),isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixturethereof.

As used herein, the term “lower aliphatic alcohols” refers to primary,secondary and tertiary monohydric and polyhydric alcohols of between 2and 12 carbon atoms. As used herein, the term “alkanes” refers tostraight chain and branched chain alkanes of between 5 and 22 carbonatoms. As used herein, the term “aromatics” refers to monocyclic,heterocyclic and polycyclic compounds. As used herein, the term“aliphatic amines” refers to primary, secondary and tertiary amineshaving alkyl substituents of between 1 and 15 carbon atoms.

In another embodiment, the solvent-extracting composition contains anorganic compound with a hydroxyl functional group.

In one embodiment, the solvent-extracting composition contains anorganic or inorganic solvent, for example, benzene, toluene, methylethyl ketone (MEK), furfural, tertrahydrofuran (THF), acetone,hydrofluoric acid, hexane and xylene, or a mixture thereof.

In another embodiment, the solvent-extracting composition contains analcohol, an organic compound with a hydroxyl functional group, and anorganic or inorganic solvent, or a combination of any two thereof. Thesolvent-extracting composition may comprise, consist essentially of, orconsist of an alcohol, an organic compound with a hydroxyl functionalgroup, and/or an organic or inorganic solvent.

In yet another embodiment, the solvent-extracting composition contains asecond liquid selected from alkanes, aromatics, aliphatic amines,aromatic amines, carbon bisulfide, vegetable oils, solvents manufacturedin petroleum refining, dry distilling coal, fractionating liquefiedcoal, and fractionating extracted hydrocarbons from tar (oil) sands andoil shale, or a mixture thereof.

In certain embodiments, the ratio of alcohol to the organic compoundwith a hydroxyl functional group or the organic or inorganic solvent inthe solvent-extracting composition to the second liquid is greater thanor equal to about 1:1 by volume. In one embodiment, the ratio of alcoholto the organic compound with a hydroxyl functional group or the organicor inorganic solvent in the solvent-extracting composition to the secondliquid is greater than or equal to about 3:1 by volume.

In another embodiment, the ratio of alcohol to the organic compound witha hydroxyl functional group or the organic or inorganic solvent in thesolvent-extracting composition to the second liquid is between about 1:5to 5:1 by volume. In one embodiment, the ratio of alcohol to the organiccompound with a hydroxyl functional group or the organic or inorganicsolvent in the solvent-removing composition to the second liquid isbetween about 1:2 to 2:1 by volume.

In one embodiment, the turpentine-extracting composition contains atleast about 10% of the acyclic or cyclic alcohol. In another embodiment,the solvent-extracting composition contains at least about 30% of theacyclic or cyclic alcohol. In another embodiment, the solvent-extractingcomposition contains at least about 50% of the acyclic or cyclicalcohol. In another embodiment, the solvent-extracting compositioncontains at least about 70% of the acyclic or cyclic alcohol. In anotherembodiment, the solvent-extracting composition contains at least about90% of the acyclic or cyclic alcohol. In another embodiment, thesolvent-extracting composition contains about 100% of the acyclic orcyclic alcohol.

In one embodiment, the quantity of the solvent trapped within the poresof the solvent-treated material or at the surface of the solvent-treatedmaterial is reduced by at least about 10% and up to about 100%. In oneembodiment, the quantity of the solvent contained within thesolvent-treated material or at the surface of the solvent-treatedmaterial is reduced by at least about 50%. In one embodiment, thequantity of the solvent contained within the solvent-treated material orat the surface of the solvent-treated material is reduced by at leastabout 75%. In one embodiment, the quantity of the solvent containedwithin the solvent-treated material or at the surface of thesolvent-treated material is reduced by about 100%.

As used herein, the term “substantially reduces” shall mean the amountof turpentine liquid contained in the solvent-treated material isreduced by at least about 50%.

The solvent-extracting composition is said to consist essentially of thealcohol, the organic compound with a hydroxyl functional group, and/orthe organic or inorganic solvent if the alcohol, the organic compoundwith a hydroxyl functional group, and/or the organic or inorganicsolvent is the essential active ingredient for substantially all of thesolvent extraction and the other ingredients in the composition areessentially inactive or non-active in solvent extraction. Thus, incertain embodiments, the basic and novel characteristics of the presentinvention include a composition consisting essentially of an alcohol,the organic compound with a hydroxyl functional group, and/or theorganic or inorganic solvent that excludes other activesolvent-extracting ingredients.

As used herein, the term “non-active” shall mean that the ingredient isnot present in an effective active amount for solvent extraction.

In another embodiment, the invention includes a method for penetratingthrough pores or the surface of a material that has previously beentreated with one or more solvents. The method includes the step ofcontacting the solvent-treated material with an amount of thesolvent-extracting composition sufficient to penetrate through the poresor the surface of the solvent-treated material.

In another embodiment, the inventive composition is substantiallynon-aqueous or the method involves contacting the solvent-treatedmaterial or its surface with a substantially non-aqueoussolvent-extracting composition. In certain embodiments, water is notused in the method. In some embodiments, salts or salt solutions are notused in the method. For example, calcium chloride is not used in someembodiments. In a preferred embodiment, the solvent-extractingcomposition or solvent-extraction method is non-aqueous. In certainembodiments, the solvent-extracting composition or solvent-extractionmethod does not use cyclo-tetramethylene sulfones, aliphatic acidamides, N-methylpyrrolidones, N-alkylated pyrrolidones, piperidones, orpolyethylene glycols. In some embodiments, the solvent-extractingcomposition or solvent-extraction/removal method does not use anemulsion for extracting/removing the solvent and any solvent associatedliquids.

In certain embodiments, the use of heating or evaporation for removingsolvent from a solvent-treated material can be avoided by using themethod described in this disclosure. Thus, in some embodiments, themethod of this disclosure does not involve evaporation of the trappedsolvent before or during contacting with the solvent-extractingcomposition.

In certain embodiments, one or more surfactants may be added to thesolvent-extraction method or the solvent-extracting composition. Yet inother embodiments, the solvent-extracting composition and process issurfactant-free or substantially surfactant-free. In certainembodiments, the solvent-extracting method or the solvent-extractingcomposition is micelle-free or substantially micelle-free.

In certain embodiments, the ratio of the solvent-extracting compositionto solvent-treated material is in a range of about 1:6 and 6:1 byweight, or in a range of about 1:2 and 4:1 by weight. In anotherembodiment the ratio of the solvent-extracting composition tosolvent-treated material is in a range of about 1:1 and 3:1 by weight.

In other embodiments, the amount of the solvent-extracting compositionused is about 10 to about 2500 wt. % of the solvent-treated material. Incertain embodiments, the amount of the solvent-extracting compositionused is about 30 to about 200 wt. % of the solvent-treated material. Inother embodiments, the amount of the solvent-extracting composition usedis about 50 to about 150 wt. % of the solvent-treated material. In oneembodiment, the amount of the solvent-extracting composition used isabout 100 wt. % of the solvent-treated material.

In certain embodiments, the dissolution, displacement, removal,recovery, liquefaction, solubilization and/or extraction of solvents canbe carried out at a temperature within the range of about 2° C. to about400° C. In certain embodiments, the solvent-treated material iscontacted with the solvent-extracting composition at a temperature ofless than about 280° C., or less than about 160° C. In otherembodiments, the dissolution, displacement, removal, recovery,liquefaction, solubilization and/or extraction temperatures can occurwithin the range of about 15° C. to about 150° C. In one embodiment, theinventive method includes boiling. In another embodiment, the inventivemethod includes boiling and refluxing the solvent-extracting compositionafter it is contacted with the solvent-treated material.

The contacting step for dissolution, displacement, removal, recovery,liquefaction, solubilization and/or extraction of the solvent-treatedmaterial can involve one or more steps including mixing, stirring,in-line static mixing, dipping, submerging, and/or any other means ofcontacting the solvent-treated material with the solvent-extractingcomposition. Boiling and refluxing of the solvent-extracting compositionmay be used, in part, to effect mixing and/or agitation. In oneembodiment, the contacting step involves penetrating thesolvent-extracting composition into the pores of the solvent-treatedmaterial.

The contacting step can occur over a period of 1 to 300 minutes. In oneembodiment, the contacting step can occur over a period of 5 to 60minutes, at a pressure between 1 and 10 atm. The contacting step may berepeated once or multiple times. For example, the contacting step may berepeated 1 to 10 times.

After contacting, the solvent-treated material is separated from thesolvent-extracting composition. Separation can occur through anysuitable means including, but not limited to, vacuum or pressurefiltration, and/or gravity separation.

The solvent can be separated from the solvent-extracting composition viaany suitable means including, but not limited to, flash evaporation, airdrying, under vacuum, air blowing, or distillation. For example, atrapped turpentine liquid can be separated from a turpentine-extractingcomposition via any suitable means.

According to an aspect of the present invention, the solvent-treatedmaterial is contacted with a heterogeneous liquid including asolvent-extracting composition. In other embodiments, thesolvent-treated material is contacted with a homogeneous, one-phaseliquid. The homogeneous, one-phase liquid can comprise, consistessentially of, or consist of the solvent-extracting composition.

In certain embodiments, the ratio of alcohol, the organic compound witha hydroxyl functional group, and/or the organic or inorganic solvent inthe solvent-extracting composition to water is greater than or equal toabout 1:1 by volume.

According to another embodiment, a method is provided including thesteps of liquefying, solubilizing and/or extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial, such as coal, oil shale, tar (oil) sands, or a reservoircontaining heavy crude oil, crude oil, natural gas (which frequentlycoexists with crude oils and other said fossil fuels), or a combinationthereof. Hydrocarbon-containing organic matter includes, but is notlimited to, heavy crude oil, crude oil, natural gas, petroleum gas, andthe like. Hydrocarbon-containing organic matter can be solid,semi-solid, liquid, sludge, viscous liquid, liquid or gaseous form.Other materials that are suitable hydrocarbon-containing materials fortreatment using the method of this invention include liquids and solidsthat include hydrocarbon-containing materials as well as a residualmaterial. Exemplary hydrocarbon-containing materials can also includeoil tank bottoms, oil pit or pond sludge and slurry mix, discardedfoods, manure, sewage sludge or municipal garbage. Liquefying,solubilizing and/or extracting the hydrocarbon-containing organic matterincludes the step of providing a hydrocarbon-extracting liquid,contacting the hydrocarbon-containing material with thehydrocarbon-extracting liquid so as to extract at least a portion ofsaid hydrocarbon-containing organic matter from saidhydrocarbon-containing material into said hydrocarbon-extracting liquidto create an extraction mixture that includes the hydrocarbon-containingorganic matter that has been removed from the hydrocarbon-containingmaterial and the hydrocarbon-extracting liquid, and separating theextracted organic matter in the hydrocarbon-extracting liquid from anyresidual material not extracted.

In one embodiment, the method includes a method of extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial by providing a hydrocarbon-extracting liquid containing aturpentine liquid, contacting the hydrocarbon-containing material withthe hydrocarbon-extracting liquid such that an extraction mixture isformed that contains at least a portion of the hydrocarbon-containingorganic matter extracted into the hydrocarbon-extracting liquid, andseparating the extraction mixture from any residual material containingnon-soluble material from the hydrocarbon-containing material that isnot soluble in the hydrocarbon-extracting liquid.

In one embodiment, the hydrocarbon-extracting liquid is substantiallysurfactant-free. In some embodiments, the hydrocarbon-extracting liquidis non-aqueous. The hydrocarbon-extracting liquid can be selected fromthe group consisting of natural turpentine, synthetic turpentine,mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol,β-terpineol, γ-terpineol, terpene resins, α-terpene, β-terpene,γ-terpene, geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol,pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol,dihydromycenol, isoborneol, p-menthan-8-ol, α-terpinyl acetate,citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal,menthol, anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and mixtures thereof.

In one embodiment, the method includes separating the extraction mixtureinto a first portion and a second portion, the first portion of theextraction mixture comprising a hydrocarbon product comprising at leasta portion of the hydrocarbon-containing organic matter, the secondportion of the extraction mixture comprising at least a portion of theturpentine liquid.

In some embodiments, the method includes recycling at least a portion ofthe turpentine liquid to the hydrocarbon-extracting liquid for use inthe contacting step.

In another aspect, a method for the recovery of hydrocarbon-containingorganic matter from a hydrocarbon-containing material is provided. Inone embodiment, the hydrocarbon-containing material can be a naturalhydrocarbon-containing material from a naturally occurring geologicalformation. Some examples of natural hydrocarbon-containing materials arecoal, crude oil, tar, tar (oil) sands, oil shale, oil sands, naturalgas, petroleum gas, crude bitumen, natural kerogen, natural asphalt, andnatural asphaltene. The method includes obtaining ahydrocarbon-containing material sample, such as by mining a formationrich in tar (oil) sands to provide a tar (oil) sands sample, wherein thehydrocarbon-containing material sample includes a recoverablehydrocarbon-containing organic matter and residual inorganic orinsoluble material. The hydrocarbon-containing material sample issupplied to a contacting vessel, wherein the contacting vessel includesat least one inlet for supplying a hydrocarbon-extracting liquid thatconsists essentially of a turpentine liquid for recovery of hydrocarbonsfrom the hydrocarbon-containing material.

The hydrocarbon-containing material sample is contacted with ahydrocarbon-extracting liquid and agitated to extract thehydrocarbon-containing organic matter from the hydrocarbon-containingmaterial to produce a residual material and an extraction mixture. Theextraction mixture includes the hydrocarbon-extracting liquid andrecovered hydrocarbon-containing organic matter, and the residualmaterial which includes at least a portion of the non-soluble material.The extraction mixture is separated from from the residual material, andis further separated into a hydrocarbon product stream and ahydrocarbon-extracting liquid stream, wherein the hydrocarbon-extractingliquid stream includes at least a portion of the hydrocarbon-containingorganic matter extracted from the hydrocarbon-containing material. Incertain embodiments, the method further includes the step of recyclingthe turpentine liquid stream to the contracting vessel. In otherembodiments, the extraction mixture can be separated by distillation toproduce the hydrocarbon product stream and the turpentine liquid recyclestream. The turpentine liquid includes at least one compound selectedfrom natural turpentine, synthetic turpentine, mineral turpentine, pineoil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In otherembodiments, the turpentine liquid includes at least one compoundselected from geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol,pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol,dihydromycenol, isoborneol, p-menthan-8-ol, a-terpinyl acetate,citronellol, p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal,menthol, and mixtures thereof. In other embodiments, the turpentineliquid includes at least one compound selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. In one embodiment, the turpentine liquidincludes at least about 30% by volume α-terpineol and at least about 25%by volume β-terpineol. In another embodiment, the turpentine liquidincludes between about 30 and 70% by volume α-terpineol, between about25 and 55% by volume β-terpineol, up to about 10% by volume a-terpene,and up to about 10% by volume β-terpene.

In another embodiment, hydrocarbon-containing organic matter, e.g., fromoil sands is extracted into the hydrocarbon-extracting liquid in anamount that corresponds to an amount of from about 85 to 100% of thehydrocarbon-containing organic matter originally contained within thesample within about 3 seconds to 3 minutes of contacting at a contactingtemperature in a range of from about 30 to 60° C. at a weight ratio ofhydrocarbon-extracting liquid to the sample of from about 1:1 to 2:1.

As shown in Table 1, the specific formulation for extraction,liquefaction and/or solubilization of hydrocarbon-containing organicmatter from tar (oil) sands varies based upon the particle size. Incertain embodiments, the method for preparing a turpentine liquid forextracting hydrocarbon-containing organic matter from tar (oil) sandsincludes adjusting the amount of α-terpineol and β-terpineol in theformulation as a function of the size of the hydrocarbon rich solidparticulate being extracted. In other embodiments, if thehydrocarbon-containing organic particulate matter includes low gradecoal or an oil shale, the amount α-terpineol in the turpentine liquid isincreased and the amount of β-terpineol in the turpentine liquid isdecreased. In other embodiments, if the hydrocarbon-containing organicparticulate matter includes tar (oil) sands, the amount α-terpineol inthe turpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased. In other embodiments, if thehydrocarbon-containing organic particulate matter includes tar (oil)sands and the mean diameter of the particulate matter is less than about4.76 mm, then the amount α-terpineol in the turpentine liquid isdecreased and the amount of β-terpineol in the turpentine liquid isincreased. In other embodiments, if the hydrocarbon-containing organicparticulate matter includes tar (oil) sands and the mean diameter of theparticulate matter is greater than about 25 mm (1 mesh), then the amountα-terpineol in the turpentine liquid is decreased and the amount ofβ-terpineol in the turpentine liquid is increased.

TABLE 1 Formulations for Extraction of Tar (oil) sands based uponParticle Size Particle Size (mm diameter) α-terpineol β-terpineolα-/β-terpene other  <5 mm 30-50% vol 35-55% vol 10% vol 5% vol 5 mm-25mm 40-60% vol 30-50% vol 10% vol 5% vol >25 mm 50-70% vol 25-45% vol 10%vol 5% vol

Similar to what is shown above with respect to the extraction of tar(oil) sands, as shown in Tables 2 and 3, the formulation for extraction,liquefaction and/or solubilization of coal depends on particle size,quality of the coal being extracted, and general operating conditions.In one embodiment of the method for preparing a turpentine liquid forextracting hydrocarbon-containing organic matter, if thehydrocarbon-containing matter includes anthracite, bituminous coal, orother high grade coal and the mean diameter of the particulate matter isless than about 0.1 mm, then the amount of α-terpineol in the turpentineliquid is decreased and the amount of β-terpineol in the turpentineliquid is increased. In other embodiments, if the hydrocarbon richparticulate matter includes anthracite, bituminous coal, or other highgrade coal and the mean diameter of the particulate matter is greaterthan about 1 mm, then the amount of α-terpineol in the turpentine liquidis decreased and the amount of β-terpineol in the turpentine liquid isincreased. In another embodiment, if the hydrocarbon rich particulatematter includes low grade coal and the mean diameter of the particulatematter is less than about 0.07 mm, then the amount of α-terpineol in theturpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased. In another embodiment, if thehydrocarbon rich particulate matter includes low grade coal and the meandiameter of the particulate matter is greater than about 0.4 mm, thenthe amount of α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased.

TABLE 2 Formulations for Extraction of High Grade Coal based uponParticle Size Particle Size (mm diameter) α-terpineol β-terpineolα-/β-terpene other <0.15 mm 45-65% vol 35-45% vol 10% vol 0% vol 0.8mm-0.15 mm 50-70% vol 20-40% vol 10% vol 0% vol  >0.8 mm 60-80% vol15-35% vol 10% vol 0% vol

TABLE 3 Formulations for Extraction of Low Grade Coal based uponParticle Size Particle Size (mm diameter) α-terpineol β-terpineolα-/β-terpene other <0.07 mm 60-80% vol 10-30% vol  5% vol 0% vol 0.07mm-0.4 mm 70-90% vol 5-25% vol 5% vol 0% vol  >0.4 mm 75-95% vol 0-20%vol 5% vol 0% vol

Similar to what is shown above with respect to the extraction of tar(oil) sands and coal, as shown in Table 4, the formulation forextraction, liquefaction and/or solubilization of oil shale depends onparticle size. In one embodiment of the method for preparing acomposition for extracting hydrocarbon-containing organic matter, if thehydrocarbon rich particulate matter includes an oil shale and the meandiameter of the particulate matter is less than about 0.074 mm, then theamount of α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased. In anotherembodiment, if the hydrocarbon rich particulate matter includes oilshale and the mean diameter of the particulate matter is greater thanabout 0.42 mm, then the amount of α-terpineol in the turpentine liquidis decreased and the amount of β-terpineol in the turpentine liquid isincreased.

TABLE 4 Formulations for Extraction of Oil Shale based upon ParticleSize Particle Size (mm diameter) α-terpineol β-terpineol α-/β-terpeneother <0.07 mm 60-80% vol 10-30% vol  5% vol 0% vol 0.07 mm-0.4 mm70-90% vol 5-25% vol 5% vol 0% vol  >0.4 mm 75-95% vol 0-20% vol 5% vol0% vol

The formulation for the extraction of crude oil similarly depends on thetype of crude oil being extracted, liquefied, and/or solubilized. Asshown in Table 5, the formulation for the extraction, liquefactionand/or solubilization of crude oil is a function of both pore size andthe quality of the density of the crude oil being extracted. The methodincludes providing a turpentine liquid formulation that includes atleast about 50% by volume α-terpineol and at least about 20% by volumeβ-terpineol; adjusting the amount of α-terpineol and β-terpineol in theturpentine liquid formulation based upon the density of the liquidhydrocarbon being extracted. In one embodiment, if the API gravity ofthe liquid hydrocarbon being extracted is greater than about 22°, thenthe amount of α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased. In anotherembodiment, if the API gravity of the liquid hydrocarbon being extractedis less than about 22, then the amount of α-terpineol in the turpentineliquid is increased and the amount of β-terpineol in the turpentineliquid is decreased. As used herein, light oils have an API of at leastabout 31°, medium crude oils have an API of between about 22° and about31°, heavy oil has an API of between about 10° and about 22°, and extraheavy oil has an API of less than about 10°.

TABLE 5 Formulations for Extraction of Crude Oil based upon API DensityCrude Type α-terpineol β-terpineol α-/β-terpene other Light/medium40-70% vol 30-40% vol 10% vol 10% vol crude (API greater than 22°)Heavy/Extra 50-70% vol 20-35% vol 10% vol  5% vol Heavy (API less than22°)

In one embodiment, this disclosure provides a method of extractinghydrocarbon-containing organic matter from oil shale or tar (oil) sandsinto turpentine liquids and/or other associated liquids and subsequentlydissolving, extracting, recovering, and/or removing turpentine liquidsand/or other associated liquids from a turpentine liquid-treatedmaterial, comprising the steps of extracting the hydrocarbon-containingorganic matter by first using a hydrocarbon-extracting liquid comprisinga non-aqueous turpentine liquid; contacting the oil shale or tar (oil)sands with a hydrocarbon-extracting liquid such that an extractionmixture is formed, the extraction mixture comprising at least a portionof hydrocarbon-containing organic matter from the oil shale or tar (oil)sands extracted into the turpentine liquid; separating the extractionmixture from a residual turpentine liquid-treated material containingnon-soluble material from the oil shale or tar (oil) sands that is notsoluble in the hydrocarbon-extracting liquid; providing asolvent-extracting composition; contacting the residual turpentineliquid-treated material containing non-soluble material from the oilshale or tar (oil) sands that is not soluble in thehydrocarbon-extracting liquid with the solvent-extracting compositionsuch that the solvent-extracting composition penetrates into pores ofthe residual turpentine liquid-treated material, forming a recoverymixture, wherein the recovery mixture has at least a portion of theturpentine liquid and any associated liquids extracted into thesolvent-extracting composition; and separating the recovery mixture fromany material containing non-extracted material from the turpentineliquid-treated material that is not extracted into thesolvent-extracting composition.

Still other aspects and advantages of the present invention will becomeeasily apparent by those skilled in the art from this description,wherein certain embodiments of the invention are shown and describedsimply by way of illustration of the best mode contemplated of carryingout the invention. As will be realized, the invention is capable ofother and different embodiments, and its several details are capable ofmodifications in various obvious respects, without departing from theinvention. Accordingly, the description is to be regarded asillustrative in nature and not as restrictive.

EXAMPLES Example 1 Extraction of Turpentine Liquid from Rubber

A crumb rubber sample having turpentine liquid trapped within its poreswas subjected to solvent extraction according to the present invention.The crumb rubber sample was initially tested and found to have about 200wt. % turpentine. The crumb rubber sample was mixed with isopropylalcohol (IPA) at a 1:1 mass ratio under ambient pressure and at about15° C. for 5 minutes. The mixing procedure was repeated twice. Afterextraction, the amount of turpentine liquid remaining in the pores ofthe crumb rubber sample was about 0.001 wt. % of the crumb rubber.

Example 2 Extraction of Turpentine Liquid from Coal

A coal sample having turpentine liquid trapped within its pores wassubjected to solvent extraction according to the present invention. Thecoal sample was initially tested and found to have about 40 wt. %turpentine. The coal sample was mixed with hexane at a 1:1 mass ratiounder ambient pressure and at about 70° C. for about 30 minutes. Themixing procedure was performed twice. After extraction, the amount ofturpentine liquid remaining in the pores of the coal sample was about 1wt. % of the coal.

Example 3 Extraction of Solvents From Rubber

Crumb rubber samples having various solvents trapped within pores weresubjected to solvent extraction according to the present invention assummarized in the below table.

Contact Solvent- Percentage of Time extracting Trapped Solvent SolventTemperature (min) Pressure Composition Extracted Para-cymene ~20° C.5-15 Ambient isopropanol 95-99% Pinene ~20° C. 5-15 Ambient isopropanol95-99% Dimethyl ~20° C. 5-15 Ambient isopropanol 95-99% sulfoxide (DMSO)Mixture of ~20° C. 5-15 Ambient isopropanol 95-99% DMSO with a blend ofturpentine liquids (30:70) Mixture of ~20° C. 5-15 Ambient isopropanol95-99% toluene with a blend of turpentine liquids (50:50) Blend of~20-40° C. 5-15 Ambient methanol 95-99% turpentine liquids Blend of~20-40° C. 5-15 Ambient ethanol 95-99% turpentine liquids Blend of~20-40° C. 5-15 Ambient propanol 95-99% turpentine liquids Blend of~20-40° C. 5-15 Ambient isopropanol 95-99% turpentine liquids Blend of~20-40° C. 5-15 Ambient butanol 95-99% turpentine liquids

Example 4 Extraction of Bitumen (Organic Matter) from Tar (Oil) Sands

Tar (oil) sands from Alberta, Canada were solubilized and extracted withcommercial grade synthetic turpentine. The tar (oil) sands sample wasobtained from Alberta Research Council, which provided the followingproximate analyses for it; 84.4 wt. % of dry solids, 11.6 wt. % of drybitumen, and 4.0 wt. % of as-received moisture. About 30 grams ofsynthetic turpentine were gently added to about 15 grams of the samplein a capped, but not tightly sealed, extraction vessel, utilizing areagent-to-sample ratio of about 2 to 1 by weight. This extractionvessel, containing the resultant mixture of synthetic turpentine and tar(oil) sands, was maintained at a constant temperature of about 96° C.and continually agitated. Without boiling of the synthetic turpentine,the pressure in the extraction vessel remained at the ambient pressureof slightly less than about 1.01×10⁵ Pascals (1 atm). After about 20minutes, the mixture in the extraction vessel was filtered and thesolids (tar (oil) sands) retained on the filter were washed with ethanoland dried to a constant weight. On the basis of weight loss, theconversion, i.e., the degree of extraction, of bitumen from the tar(oil) sands sample was determined to be about 100 wt. %.

Example 5 Extraction of Bitumen (Organic Matter) from Tar (Oil) Sands

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the precedingexample were extracted by about 60 grams of α-terpineol, instead ofcommercial-grade synthetic turpentine, which includes α-terpineol. Theresultant reagent-to-sample ratio was 1 to 1 instead of 2 to 1 as in thepreceding example. The experiment lasted about 30 minutes at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The conversion, i.e., the extent ofextraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 100 wt. %.

Example 6 Extraction of Bitumen (Organic Matter) from Tar (Oil) Sands

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the preceding twoexamples were extracted by about 60 grams of synthetic turpentine, whichis of the commercial grade. The resultant reagent-to-sample ratio,therefore, was about 1 to 1. The experiment was carried out for about 30minutes at the temperature of about 96° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The conversion, i.e.,the degree of extraction, of bitumen (organic matter) in the tar-sandssample was determined to be about 70 wt. %.

Example 7

The experiment in this example was carried out under the ambientpressure of slightly less than about 1.01×10⁵ Pascals (1 atm) with thetar-sands sample from the same source with the same proximate analysesas those in the preceding examples with tar (oil) sands. About 60 gramsof commercial-grade synthetic turpentine was added to about 60 grams ofthe tar-sands sample, thus giving rise to the reagent-to-sample ratio ofabout 1 to 1. The temperature of the sample and commercial-gradesynthetic turpentine was maintained at about 65° C. for about 30 minutesfollowed by cooling to about 15° C. within about 5 minutes.Subsequently, the tar-sands sample was filtered, washed, dried andweighed. On the basis of weight loss, the conversion, i.e., the degreeof extraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 70 wt. %.

Example 8

The experiment in this example repeated that of the preceding examplewith α-terpineol instead of commercial grade synthetic turpentine. Theconversion, i.e., the degree of extraction, of bitumen (organic matter)increased to about 90 wt. % from about 70 wt. % of the precedingexamples.

Example 9

In this example, a tar-sands sample, weighing about 30 grams, from thesame source with the same proximate analyses as those in Examples 11through 17, was extracted with a liquid that included about 20 grams (80wt. %) of α-terpineol and about 5 grams (20 wt. %) of toluene at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The duration of the experiment(reaction or extraction time) was about 30 minutes. The weigh loss ofthe sample was about 10.2 grams. From this weigh loss, the conversion,i.e., the degree of extraction, of bitumen (organic matter) wasestimated to be about 33 wt. %.

Example 10

Three tar-sands samples, all from the same source with the sameproximate analyses as those used in all preceding examples with tar(oil) sands were extracted by reagents comprising various amounts ofα-terpineol and ethanol at the temperature of about 15° C. under theambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm).The duration of each experiment (reaction or extraction time) was about15 minutes for each tar-sands sample. The first sample was extractedwith a mixture comprising about 0 gram (0 wt. %) of α-terpineol andabout 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol. Thesecond sample was extracted with a mixture comprising about 7.5 grams(50 wt. %) of α-terpineol and about 7.5 grams (50 wt. %) of ethanol. Thethird sample was extracted with a mixture comprising about 12 grams (80wt. %) of α-terpineol and about 3 grams (20 wt. %) of ethanol. Theweight losses and the estimated conversions, i.e., the degrees ofextraction, of bitumen (organic matter) in the three samples were about0.2 gram (1.0 wt. %), 0.6 gram (3.0 wt. %) and 0.9 gram (4.5 wt. %), forthe first, second and third sample, respectively.

Example 11

Irregular-shaped pellets of commercial-grade asphalt whose average sizewas about 15 mm were solubilized and extracted with α-terpineol and atthe ambient temperature of about 22° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The first sampleweighing about 20 grams was solubilized and extracted with about 40grams of α-terpineol, and the second sample also weighing about 20 gramswas solubilized and extracted with about 20 grams of α-terpineol. Thehydrocarbons in both samples were completely extracted after 30 minutes.These experiments were carried out to simulate the solubilization andextraction of heavy crude oil, which tends to be rich in asphalteneslike asphalt.

Example 12

In this example, bitumen (organic matter) in tar-sands from the samesource with the same proximate analyses as those used in all previousexamples with tar (oil) sands was solubilized and extracted with twovarieties of vegetable oils, soybean oil and corn oil. The vegetableoils are completely miscible with turpentine liquid. In the firstexperiment, a tar-sands sample weighing about 15 grams was blended andagitated continually with about 30 grams of soybean oil for about 20minutes at the temperature of about 96° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The weight loss wasabout 0.5 gram from which the conversion, i.e., the degree ofextraction, of bitumen in the sample was estimated to be about 3.3 wt.%. In the second experiment, a tar-sands sample weighing about 30 gramswas blended and agitated continually with about 60 grams of corn oil forabout 30 minutes at the temperature of about 175° C. under the ambientpressure of slightly less than about 1.01×10⁵ Pascals (1 atm). Theweight loss was about 4.8 grams from which the conversion, i.e., thedegree of extraction, of bitumen in the sample was estimated to be about12 wt. %.

Example 13

Two tests were performed on Berea sandstone plug core samples todetermine the effect of reagent injection on oil recovery from core. Thefirst test was designed to determine the increment oil recovery due toα-terpineol injection after a field had already undergone waterfloodingto the limit. The selected core contained 9.01 mL of laboratory oilsimulating crude oil. The waterflooding with aqueous solution containing3.0% of potassium chloride produced 4.6 mL of oil. Five (5) pore volumesof α-terpineol injection produced additional 3.61 mL of oil, therebyleaving the core with less than 8.0% of oil remaining in the originalvolume. The second test was designed to represent the increased recoverythat could be expected from a virgin reservoir with α-terpineolinjection. The selected core contained 8.85 mL of laboratory oilsimulating crude oil. Oil production began after approximately 0.5 porevolumes of α-terpineol injection, and continued until 3.5 pore volumesof α-terpineol had been injected; however, the majority of the oil wasrecovered after only 2.5 pore volumes of α-terpineol injection. A totalof 7.94 mL of laboratory oil was recovered, thereby leaving the corewith less than 7.5% of oil remaining in the original volume.

In one experiment, various ratios of a turpentine liquid to tar (oil)sands sample were tested. The turpentine liquid for each of theexperiments provided below had the same formulation, wherein thecomposition included about 60% by volume α-terpineol, about 20% byvolume β-terpineol, and about 20% by volume γ-terpineol. The tar (oil)sands were a different mix of ores from Alberta, Canada, having abitumen content of approximately 12% by weight and a water content ofbetween about 4-5% by weight. The experiments were all performed atvarious temperatures as listed in Table 6.

As shown in Table 6 below, recovery of hydrocarbons from tar (oil) sandsacross all ratios provided below (i.e., ratios of turpentine liquid totar (oil) sands ranging from about 1:2 to about 2:1) resulted in goodrecovery of hydrocarbons and little discernible difference. With respectto the temperature at which the extraction is carried out, it isbelieved that the optimum temperature for the extraction, solubilizationand/or liquefaction of hydrocarbons from tar (oil) sands is about 65° C.As shown in Table 6, at about 130° C., the amount of hydrocarbonsrecovered from the tar (oil) sands is reduced. It is noted however, thatfor certain solids from which it is particularly difficult to recoverhydrocarbons, increasing the temperature of the extraction solvent canincrease the amount of hydrocarbons that are recovered. Finally, it isshown that exposure time had very little effect on the amount ofmaterials that were extracted. This is likely because the shortestextraction time was about 20 minutes, which is believed to be more thanadequate for the extraction of the hydrocarbons from tar (oil) sands.

TABLE 6 Ratio of Tar (oil) Weight of tar (oil) Amount Percent Exposuresands Extractable extraction sands to of HC HC Temp, Time, Weight, g HCweight, g solvent solvent extracted, g extracted ° C. minutes 15 2.030.0 1:2 3.2 161 96 20 60 7.8 120.0 1:2 5.4 69 96 30 60 7.8 31.6 2:1 9.6123 96 30 60 7.8 60.0 1:1 7.6 97 65 30 60 7.8 60.0 1:1 4.0 51 130 30 607.8 60.0 1:1 6.3 80 65 30

Additional experiments were conducted using alternative solvents, namelyethanol and corn oil, which was compared with the composition thatincluded about 60% by volume α-terpineol, about 20% by volumeβ-terpineol, and about 20% by volume γ-terpineol. As noted in Table 7provided below, the performance of ethanol and corn oil wereunexpectedly substantially lower than the composition that includedabout 60% by volume α-terpineol, about 20% by volume β-terpineol, andabout 20% by volume γ-terpineol. For example, whereas the terpineolcomposition achieved complete or nearly complete extraction ofextractable hydrocarbons, ethanol yielded only about 10% of therecoverable hydrocarbons and heated corn oil yielded only about 33% ofthe recoverable hydrocarbons.

TABLE 7 Ratio of Tar (oil) Weight of tar (oil) Amount Percent Exposuresands Extractable extraction sands to of HC HC Temp, Time, ChemicalWeight, g HC weight, g solvent solvent extracted, g extracted ° C.minutes Ethanol 15 2.0 15.0 1:1 o.2 10 15 15 Corn oil 30 3.9 60.0 2:11.3 33 175 30 60/20/20 60 7.8 60.0 1:1 7.6 97 65 30 terpineol 60/20/2060 7.8 31.6 2:1 9.6 123 96 30 terpineol

As shown in Table 8 below, the performance of various turpentine liquidformulations, including turpentine liquid formulations that include onlyα-terpineol and α-terpineol in combination with various known organicsolvents, are provided. The first three compositions presented in thetable include α-terpineol, β-terpineol, and γ-terpineol. For example,the first same includes about 60% by volume α-terpineol, about 30% byvolume β-terpineol, and about 10% by volume γ-terpineol. The resultsunexpectedly show that as the concentration of the α-terpineolincreases, performance of the turpentine liquid increases to the pointthat when the turpentine liquid includes approximately 70% α-terpineol,full extraction of the hydrocarbon material from the tar (oil) sandssample is achieved.

The second set of data is presented for extraction of hydrocarbonbearing tar (oil) sands with pure α-terpineol. As shown, extraction ofgreater than 100% is achieved, likely due to inconsistencies in thehydrocarbon content of the samples. However, the results generallydemonstrate the unexpected result that α-terpineol is capable ofextracting substantially all of the recoverable hydrocarbon from a tar(oil) sands sample.

The data provided in Table 8 illustrates the effectiveness of mixedsystems of α-terpineol and known organic solvents. As shown,substantially complete recovery of recoverable hydrocarbons is achievedwith a composition that includes about a 1:1 ratio of α-terpineol toethanol. This is unexpected as pure ethanol only removed about 10% ofthe total recoverable hydrocarbons. Additionally, mixed systems thatinclude either a 1:1 or a 3:1 ratio of α-terpineol to toluene stillresulted in the recovery of about 77% and 92% of the total recoverablehydrocarbons. This was an unexpected result.

TABLE 8 Ratio of Tar (oil) tar (oil) Amount Percent Exposure Chemicalsands Extractable Wt. of sands to of HC HC Temp, Time, comp. wt., g HCwt., g solvent solvent extracted, g extracted ° C. minutes 60/30/10 α-60 2.0 60.0 1:1 7.1 91 96 30 terpineol/ β-terpineol/ and γ- terpineol40/30/20 α- 60 7.8 60.0 1:1 4.7 60 96 30 terpineol/ β-terpineol/ and γ-terpineol 70/20/10 α- 60 7.8 60.0 1:1 7.9 101 96 30 terpineol/β-terpineol/ and γ- terpineol 100% α- 60 7.8 60.0 1:1 10.0 128 96 30terpineol 100% α- 60 7.8 120.0 1:2 8.7 111 96 30 terpineol 100% α- 607.8 31.0 2:1 9.6 123 96 30 terpineol 50% α- 15 2.0 15.0 1:1 8.1 103 6530 terpineol/ 50% ethanol 80% α- 15 2.0 15.0 1:1 1.2 62 15 15 terpineol/20% ethanol 75% α- 30 3.9 25.0  1:0.8 1.8 92 15 15 terpineol/ 25%toluene 50% α- 30 3.9 26.0  1:0.9 3.0 77 96 30 terpineol/ 50% toluene50% α- 30 3.9 26.0  1:0.9 2.4 61 96 30 terpineol/ 50% xylenes

Example 14

Approximately 30 g tar (oil) sands samples were sprayed with each of thefollowing liquids: d-limonene, a blend of turpentine liquids, and wateras a control. Temperature was maintained at about 18° C. The percent ofbitumen recovered was measured after a contact time of about 5, 10, 15,20, 25, and 30 seconds. The blend of turpentine liquids was a moreeffective extractor than d-limonene, whereas water was ineffective (seeFIG. 5).

Example 15

Approximately 15 g tar (oil) sands samples were sprayed with d-limoneneor a blend of turpentine liquids and left in contact with the liquid for97 seconds. The ratio of liquid to tar (oil) sands ranged fromapproximately 1:1 to approximately 6:1. From 54% recovery at 1:1 to 84%recovery at 6:1 ratios, the blend of turpentine liquids extracted morebitumen than the limonene across the range of mixing ratios (see FIG.6).

Example 16

The effectiveness of a number of turpentine liquid species andcombinations for extracting hydrocarbon was measured relative to theability of each liquid to recover bitumen from a tar (oil) sands sample.In each test, an approximately 15 g tar (oil) sands sample was treatedat about 18° C. with one of the following turpentine liquids:α-terpineol, β-terpineol, β-pinene, α-pinene p-cymene, d-limonene, and ablend of turpentine liquids. The percent of bitumen recovered wasmeasured after contact times of about 5 (FIG. 7) and about 15 (FIG. 8)minutes. The data show that all of the liquids extracted a substantialamount of the bitumen from the tar (oil) sands. The blend of turpentineliquids was the most effective extractor across the range of liquid tomaterial ratios, recovering nearly all of the bitumen content withinabout 5 minutes of contact (see FIG. 7).

As measured herein, the recovery, i.e., yield, in certain samplesexceeds 100% because certain hydrocarbon-containing materials, e.g., tar(oil) sands, include heterogeneous and impure mixtures of exceedinglyviscous liquid and relatively coarse solid particles, irregular in shapeand varying in size. Thus, recovery measurements based on the averagevalue of hydrocarbon matter in the hydrocarbon-containing materials attimes exceed 100% due to these naturally variable factors. Further, someexperimental errors are inherent to any experiment.

The results for the extraction of turpentine liquid from turpentineliquid-treated material described in the specification, and especiallyin the Examples above, were unexpected. Surprising advantages wererealized in economic efficiencies achieved through practicing theclaimed invention.

As used herein, the terms about and approximately should be interpretedto include any values which are within 5% of the recited value.Furthermore, recitation of the term about and approximately with respectto a range of values should be interpreted to include both the upper andlower end of the recited range. As used herein, the terms first, second,third and the like should be interpreted to uniquely identify elementsand do not imply or restrict to any particular sequencing of elements orsteps.

While the invention has been shown or described in only some of itsembodiments, it should be apparent to those skilled in the art that itis not so limited, but is susceptible to various changes withoutdeparting from the scope of the invention.

The invention claimed is:
 1. A method for dissolving, displacing,extracting, recovering, and/or removing a solvent and solvent-associatedliquids trapped within pores of a solvent-treated material selected fromthe group consisting of a solvent-treated rubber, a solvent-treatedplastic, and a solvent-treated combination thereof, comprising the stepsof: a) providing a solvent-extracting composition, b) contacting saidsolvent-treated material with said solvent-extracting composition suchthat said solvent-extracting composition penetrates into pores of saidsolvent-treated material, c) forming a recovery mixture, wherein therecovery mixture comprises at least a portion of the solvent andsolvent-associated liquids extracted into the solvent-extractingcomposition; and d) separating the recovery mixture from material thatis not extracted into the solvent-extracting composition, wherein saidsolvent-extracting composition comprises an alcohol.
 2. The method ofclaim 1, further comprising the step of: separating the recovery mixtureinto a first portion and a second portion, the first portion comprisinga solvent product stream that includes at least a portion of the solventand any solvent-associated liquids extracted from the pores of thesolvent-treated material, the second portion comprising at least aportion of the solvent-extracting composition.
 3. The method of claim 1,wherein said solvent is a turpentine liquid, an alkane, an aromatic, analiphatic amine, an aromatic amine, carbon bisulfide or a mixturethereof.
 4. The method of claim 3, wherein said turpentine liquid isselected from the group consisting of natural turpentine, syntheticturpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene,alpha-terpineol, beta-terpineol, gamma-terpineol, 3-carene, anethole,dipentene (p-mentha-1,8-diene), terpene resins, alpha-terpene,beta-terpene, gamma terpene, nopol, pinane, camphene, p-cymene,anisaldehyde, 2-pinane hydroperoxide, 3,7-dimethyl-1,6-octadiene,isobornyl acetate, terpin hydrate, ocimene, 2-pinanol, dihydromyrcenol,isoborneol, alloocimene, alloocimene alcohols, geraniol,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, p-menthan-8-ol,alpha-terpinyl acetate, citral, citronellol,7-methoxydihydrocitronellal, 10-camphorsulphonic acid, p-menthene,p-menthan-8-yl acetate, citronellal, 7-hydroxydihydrocitronellal,menthol, menthone, polymers thereof, and mixtures thereof.
 5. The methodof claim 1, wherein said solvent-extracting composition comprises one ormore acyclic or cyclic alcohols.
 6. The method of claim 1, wherein saidsolvent-extracting composition comprises methanol, ethanol, propanol,isopropanol, butanol, isobutanol, pentanol, 1-Pentanol,3-Methyl-1-butanol, 2-Methyl-1-butanol, 2,2-Dimethyl-1-propanol,3-Pentanol, 2-Pentanol, 3-Methyl-2-butanol, 2-Methyl-2-butanol, hexanol,1-Hexanol, 2-Hexanol, 3-Hexanol, 2-Methyl-1-pentanol,3-Methyl-1-pentanol, 4-Methyl-1-pentanol, 2-Methyl-2-pentanol,3-Methyl-2-pentanol, 4-Methyl-2-pentanol, 2-Methyl-3-pentanol, Tertiary3-Methyl-3-pentanol, Primary 2,2-Dimethyl-1-butanol,2,3-Dimethyl-1-butanol, 3,3-Dimethyl-1-butanol, 2,3-Dimethyl-2-butanol,3,3-Dimethyl-2-butanol, 2-Ethyl-1-butanol, lower aliphatic alcohols or amixture thereof.
 7. The method of claim 1, wherein saidsolvent-extracting composition comprises methanol, ethanol, propanol,isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixturethereof.
 8. The method of claim 1, wherein said solvent-extractingcomposition further comprises a second liquid selected from alkanes,aromatics, aliphatic amines, aromatic amines, carbon bisulfide,vegetable oils, solvents manufactured in petroleum refining, drydistilling coal, fractionating liquefied coal, and fractionatingextracted hydrocarbons from tar (oil) sands and oil shale, or a mixturethereof.
 9. The method of claim 8, the ratio of alcohol in thesolvent-extracting composition to the second liquid is greater than orequal to about 1:1 by volume.
 10. The method of claim 1, wherein saidsolvent-treated material is contacted with said solvent-extractingcomposition in a ratio range of about 1:6 to 6:1 by weight.
 11. Themethod of claim 10, wherein the solvent-treated material is contactedwith said solvent-extracting composition in a ratio of about 1:4 to 2:1by weight.
 12. The method of claim 10, wherein the solvent-treatedmaterial is contacted with said solvent-extracting composition in aratio of about 1:3 to 1:1 by weight.
 13. The method of claim 1, whereinthe amount of the solvent-extracting composition in said recoverymixture is about 10 to about 2500 wt. % of the solvent-treated material.14. The method of claim 13, wherein the amount of the solvent-extractingcomposition in said recovery mixture is about 30 to about 200 wt. % ofthe solvent-treated material.
 15. The method of claim 14, wherein theamount of the solvent-extracting composition in said recovery mixture isabout 50 to about 150 wt. % of the solvent-treated material.
 16. Themethod of claim 15, wherein the amount of the solvent-extractingcomposition in said recovery mixture is about 100 wt. % of thesolvent-treated material.
 17. The method of claim 1, wherein saidcontacting is carried out at a temperature within the range of about 2°C. to about 400° C.
 18. The method of claim 17, wherein said contactingis carried out at a temperature within the range of about 15° C. toabout 150° C.
 19. The method of claim 1, wherein said solvent-treatedmaterial is contacted with said solvent-extracting composition for 1 to300 minutes.
 20. The method of claim 19, wherein said solvent-treatedmaterial is contacted with said solvent-extracting composition for 5 to60 minutes.
 21. The method of claim 1, wherein said contacting step (b)is repeated 1 to 10 times step (c).
 22. The method of claim 1, whereinsaid solvent-extracting composition comprises at least 10% alcohol. 23.The method of claim 1, wherein said solvent-extracting compositioncomprises at least 50% alcohol.
 24. The method of claim 1, wherein saidsolvent-extracting composition comprises at least 90% alcohol.
 25. Themethod of claim 1, wherein said contacting extracts at least 50% ofsolvent and any solvent-associated liquids contained within saidsolvent-treated material before said contacting.
 26. The method of claim25, wherein said contacting extracts at least 80% of solvent and anysolvent-associated liquids contained within said solvent—treatedmaterial before said contacting.
 27. The method of claim 1, wherein saidcontacting further comprises boiling and refluxing saidsolvent-extracting composition.
 28. The method of claim 1, wherein saidmethod comprises contacting said solvent-treated material with asubstantially non-aqueous solvent-extracting composition.
 29. The methodof claim 1, wherein said method does not involve the use of water or anemulsion.
 30. The method of claim 1, wherein said method does notinvolve the use of salt or salt solution.
 31. The method of claim 1,wherein said solvent-extracting composition comprises a surfactant. 32.The method of claim 1, wherein said solvent-extracting composition issurfactant-free or substantially surfactant-free.
 33. The method ofclaim 1, wherein said solvent-extracting composition is micelle-free orsubstantially micelle-free.
 34. The method of claim 1, wherein saidsolvent is a decant oil, a light cycle oil, naphta, benzene,naphthalene, toluene, pentane, heptane, hexane, xylene, anthracene,tetraline, triethylamine, aniline, carbon bisulfide, or a mixturethereof.